Abstract

We describe magic-angle-spinning NMR methods for the accurate determination of internuclear dipole−dipole couplings between homonuclear spins-1/2 in the solid state. The new sequences use symmetry principles to treat the effect of magic-angle sample-rotation and resonant radio frequency fields. The pulse-sequence symmetries generate selection rules which reduce the interference of undesirable interactions and improve the robustness of the pulse sequences with respect to chemical shift anisotropies. We show that the pulse sequences may be used to estimate distances between 13C spins in organic solids, including bond lengths in systems with large chemical shift anisotropies, such as conjugated systems. For bond-length measurements, the precision of the method is ±2 pm with a systematic overestimate of the internuclear distance by 3 ± 1 pm. The method is expected to be a useful tool for investigating structural changes in macromolecules.